The oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating "high aspect ratio" LaNiO and LaMnO nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. We observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO.
PURPOSE Photon involved-field radiotherapy (IFRT) is the standard-of-care radiotherapy for patients with leptomeningeal metastasis (LM) from solid tumors. We tested whether proton craniospinal irradiation (pCSI) encompassing the entire CNS would result in superior CNS progression-free survival (PFS) compared with IFRT. PATIENTS AND METHODS We conducted a randomized, phase II trial of pCSI versus IFRT in patients with non–small-cell lung cancer and breast cancers with LM. We enrolled patients with other solid tumors to an exploratory pCSI group. For the randomized groups, patients were assigned (2:1), stratified by histology and systemic disease status, to pCSI or IFRT. The primary end point was CNS PFS. Secondary end points included overall survival (OS) and treatment-related adverse events (TAEs). RESULTS Between April 16, 2020, and October 11, 2021, 42 and 21 patients were randomly assigned to pCSI and IFRT, respectively. At planned interim analysis, a significant benefit in CNS PFS was observed with pCSI (median 7.5 months; 95% CI, 6.6 months to not reached) compared with IFRT (2.3 months; 95% CI, 1.2 to 5.8 months; P < .001). We also observed OS benefit with pCSI (9.9 months; 95% CI, 7.5 months to not reached) versus IFRT (6.0 months; 95% CI, 3.9 months to not reached; P = .029). There was no difference in the rate of grade 3 and 4 TAEs ( P = .19). In the exploratory pCSI group, 35 patients enrolled, the median CNS PFS was 5.8 months (95% CI, 4.4 to 9.1 months) and OS was 6.6 months (95% CI, 5.4 to 11 months). CONCLUSION Compared with photon IFRT, we found pCSI improved CNS PFS and OS for patients with non–small-cell lung cancer and breast cancer with LM with no increase in serious TAEs.
Adsorptive separation by porous solids provides an energy-efficient alternative for the purification of important chemical species compared to energy-intensive distillations. Particularly, the separation of linear hexane isomers from its branched counterparts is crucial to produce premium grade gasoline with high research octane number (RON). Herein, we report the synthesis of a new, flexible zinc-based metal–organic framework, [Zn5(μ3-OH)2(adtb)2(H2O)5·5 DMA] (Zn-adtb), constructed from a butterfly shaped carboxylate linker with underlying (4,8)-connected scu topology capable of separating the C6 isomers nHEX, 3MP, and 23DMB. The sorbate–sorbent interactions and separation mechanisms were investigated and analyzed through in situ FTIR, solid state NMR measurements and computational modeling. These studies reveal that Zn-adtb discriminates the nHEX/3MP isomer pair through a kinetic separation mechanism and the nHEX/23DMB isomer pair through a molecular sieving mechanism. Column breakthrough measurements further demonstrate the efficient separation of linear nHEX from the mono- and dibranched isomers.
Predicting drug release profiles from polymer microparticles has proven challenging due to the numerous environmental and chemical factors that affect the device and influence the rate of drug release. By measuring the various polymer properties that can influence drug release, a predictive approach can be used to select polymers with specific properties that will lead to the desired release profile for the application. To illustrate this, a library of tyrosol-derived poly(ester-arylate)s, poly(amide)s, and poly(carbonate)s were used to evaluate the effects of physical (crystallinity, water accessibility, thermal, and hydrophobicity) and chemical (polymer−drug interactions) polymer properties on the release of a highly crystalline drug dexamethasone, which was loaded at a high weight percent (wt %) in microparticles. Nuclear magnetic resonance (NMR) experiments showed that the polymer and drug were not chemically interacting and instead exist as a physical mixture even after exposure to physiological conditions. Polymer crystallinity data revealed that crystallite size was strongly correlated with faster drug release, suggesting that larger crystallites reduce the tortuosity for dexamethasone to diffuse out of the particle matrix. This correlation observed in particles with and without the drug was reproduced with bulk polymers, indicating that crystallinity data from bulk polymers can be used to predict release profiles without having to prepare drug-loaded particles. Consistent with the crystallinity data, particle pore sizes of representative formulations showed that particles with larger pores resulted in faster dexamethasone release. Interestingly, thermal properties (glass transition temperature and melting temperature), polymer hydrophobicity, and molecular weight retention at the end of the 119-day release study did not show any correlation with drug release.
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